US5855959A - Process for providing catalytically active platinum metal layers - Google Patents

Process for providing catalytically active platinum metal layers Download PDF

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Publication number
US5855959A
US5855959A US08/042,303 US4230393A US5855959A US 5855959 A US5855959 A US 5855959A US 4230393 A US4230393 A US 4230393A US 5855959 A US5855959 A US 5855959A
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process according
platinum metal
solution provided
nickel
acid
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US08/042,303
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Inventor
Juergen Boecker
Michael Butz
Alfred Frey
Petra Hofmeister
Hans Dieter Schmidt
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International Business Machines Corp
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International Business Machines Corp
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Priority to US08/443,132 priority Critical patent/US5624479A/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Definitions

  • the invention relates to catalytically active platinum metal layers.
  • Platinum metals is the generic term for the metals of subgroup VIII of the periodic table of the elements and comprises: Ru, Rh, Pd, Os, Ir and Pt. These metals are used in various chemical processes due to their catalytic properties. Examples of processes utilizing platinum metal catalysts are hydrogenation processes, e.g. in oil and grease production and chemical synthesis, like the Fischer-Tropsch reaction, or in environmental protection, e.g. car catalysts or water cleaning. Another example of the use of platinum metal catalysts is in plating processes where they serve as a seed layer for the deposition of metal ions on dielectric or metallic surfaces.
  • the catalytic activity of a platinum metal seed layer depends on the nature of the surface of the platinum metal layer, i.e., the smaller the seeds and the greater their number, the better is the catalytic activity. This is true of all of the platinum metal catalyst applications cited above.
  • a platinum metal is conventionally deposited onto a surface from an acidic solution containing a platinum metal salt. This standard procedure is known to result in unsatisfactory platinum metal layers having undesirable irregularities and inhomogeneous thicknesses. Also, the catalytic activity of these conventionally deposited platinum metal layers has been found to be insufficient for various applications.
  • a. providing an activator compound homogeneously distributed in a solvent, the activator compound being an ionogenic compound capable of releasing platinum metal ions, the solvent being an organic and/or inorganic acid solution;
  • step c.) applying the solution provided in step b.) to a surface to be catalyzed.
  • This invention relates to the deposition of platinum metal layers on various surfaces, e.g. dielectric or metallic surfaces.
  • the invention is described in the following in connection with a method for selectively chemically depositing metals such as nickel, cobalt, iron, copper or alloys thereof over existing metallurgy patterns on a dielectric substrate, and to products produced thereby. More particularly, the invention is described in connection with the electroless plating of nickel over metallurgy patterns on ceramic substrates in high-circuit-density electronic components.
  • an important application of the present invention relates to the fabrication of multilayer ceramic modules used in semiconductor package assemblies and, more particularly, to the simultaneous chemical deposition, by electroless plating procedures, of essentially crack-free nickel of uniform thickness onto a plurality of discrete and electrically isolated contact pads on such modules, as well as onto the seal areas which surround such contact pads.
  • this application of the invention results in nickel layers with improved solderability, brazability, and wire and diode bonding properties as well as seal areas with improved hermetic sealing characteristics.
  • a multilayer ceramic substrate be formed with circuit lines and via holes having very small dimensions, such microminiaturization being desirable in order that the corresponding electronic package be compatible with the integrated circuit device chips which are to be mounted thereon.
  • the module therefore, must be provided on the top surface with many small pads which are closely spaced but electrically isolated from each other and capable of making electrical contact with correspondingly closely spaced terminal devices.
  • As many integrated circuit devices as possible are supported and interconnected by the same module. This arrangement keeps the distance between the interconnected devices small and thereby minimizes the time it takes for electrical signals to travel from interrelated devices.
  • this arrangement also reduces the number of electrical interconnections which must be made and thereby reduces the cost of the package and increases its reliability.
  • the desirable end result is a highly complex multi-layer ceramic package with a substantial amount of microsized internal printed circuitry supporting and electrically interconnecting a relatively large number of integrated circuit devices.
  • Multi-layer ceramic modules require complex metallurgy (i.e. the fabrication of relatively thin metallurgy layers) on the top-side to make connections to the integrated circuit devices and provide engineering change pads, and on the bottom-side to make connection to the I/O pads or other types of connections. In the next paragraphs it is shown how this metallurgy is provided on the modules.
  • the metallurgy pattern on the top-side surface of a (green) multi-layer ceramic module is formed, for example, by screen printing a conductive paste of a molybdenum-containing compound onto the top-side surface.
  • the module is then sintered, and the top-side surface of the module is cleaned to remove any contaminants thereon, typically by a suitable alkaline cleaning operation. That surface is then treated to remove traces of the conductive paste from the areas between the individual circuit elements. While this step can be accomplished in a number of different ways apparent to those skilled in the art, one suitable procedure involves the application to such surface of a solution of potassium ferricyanide and potassium hydroxide, typically in a ratio of two parts of potassium ferricyanide for each part of potassium hydroxide. This step not only functions to remove traces of the conductive material which could produce short circuiting between the electrical contact pads, but also serves to activate the surface of such contact pads for subsequent plating.
  • the top-side surface of a ceramic module is immersed in the above-described solution for a period of from about 30 to about 50 seconds at room temperature.
  • the surface is then rinsed to remove all traces of the alkaline solution, usually a one minute rinse with deionized water is sufficient.
  • Traces of glass from the conductive paste deposits are now removed by immersion of the top-side surface in a hot caustic solution such as a solution of 100 g per liter of potassium hydroxide at 100° C. for a period of from 10 to 15 minutes. If this treatment time is not sufficient, the amount of metal which is exposed may be insufficient for satisfactory plating adhesion. On the other hand, if treatment time is longer than necessary, a weakened plating bond may result. Thereafter, residual quantities of the potassium hydroxide are removed by suitable rinsing, for example with deionized water.
  • Surface preparation is preferably followed by dipping the top-side surface to be ultimately plated in an acid solution such as, for example, a hydrochloric acid solution having a concentration of from 1 to 10 percent by weight for a period of from 6 to 10 seconds to remove any metal oxides. Any residual hydrochloric acid remaining is removed by rinsing, again with deionized water or other suitable washing agent.
  • an acid solution such as, for example, a hydrochloric acid solution having a concentration of from 1 to 10 percent by weight for a period of from 6 to 10 seconds to remove any metal oxides. Any residual hydrochloric acid remaining is removed by rinsing, again with deionized water or other suitable washing agent.
  • the thus prepared metallurgy pattern defined by the conductive paste is now ready to be catalyzed, that is, to make such surface receptive to accept the reduction of nickel ions by a boron containing reducing agent in the electroless bath of the chemical plating step and to accept such deposits as a uniform layer on these surfaces.
  • Preferred catalyzing agents are platinum metal salts, such as chlorides, sulphates, acetates etc., (e.g. PdCl 2 or PtCl 2 ) which typically can be employed in an aequous solution of from about 0.01 to about 1, and preferably about 0.1, percent of platinum metal chloride.
  • This solution is rendered acidic by the addition of organic and/or inorganic acids, like HCl, H 2 SO 4 , CH 3 COOH or CCl 3 COOH until a pH of about 0.1 to about 3.0, preferably from about 1.0 to about 2.0, is reached.
  • organic and/or inorganic acids like HCl, H 2 SO 4 , CH 3 COOH or CCl 3 COOH until a pH of about 0.1 to about 3.0, preferably from about 1.0 to about 2.0, is reached.
  • a sulfonic acid is added to the above-mentioned catalyzing agent. It is important that the sulfonic acid be added in the form of an alkali-free acid and not in the salt form.
  • Suitable sulfonic acids are arylsulfonic acids, alkylsulfonic acids or arylalkylsulfonic acids with branched or unbranched chains or mixtures thereof.
  • the sulfonic acid is added to the platinum metal salt in a molar ratio of about 1:1 and this solution is homogenized. An actual optimum concentration of platinum metal will vary in accordance with the conditions of metallization and the particular chemical compounds selected for specific applications.
  • the surface to be catalyzed is then dipped into the platinum metal chloride solution containing the sulfonic acid for about 30 to about 80 seconds. This is done at temperatures from about 0° C. to about 80° C., preferably at about room temperature.
  • the catalytic activity of the platinum metal layer deposited according to the present invention is about 40 to about 80 percent greater than without the additon of sulfonic acid and about 30 to about 40 percent greater than with sulfonate added.
  • This is achieved with the same quantity of the catalyzing agent, with an increased number of seeds per ⁇ m 2 (70 with the addition of sulfonic acid versus 20 with standard activation) and a seed size which is below the detection limit of field emission scanning electron microscopes.
  • the surface of the catalizing agent layer is largely increased.
  • the seed distribution is very homogenous over the surface.
  • DMAB autocatalytic dimethylamine borane
  • the higher surface density of the catalytic seeds leads to a "screening" of the molybdenum layer and thereby avoids corrosion thereof.
  • platinum metal chloride solution Another advantageous benefit obtained with such a platinum metal chloride solution is that it becomes absorbed on the conductive paste and is reduced thereon to the metal, a strong catalyst, while the platinum metal chloride which comes into contact with the dielectric or ceramic surface and may be present after rinsing, remains as platinum metal chloride, a relatively weak catalyst. Accordingly, during subsequent plating there is a greater tendency for the nickel to be deposited onto the contact pads and seal blank area and to thereby assure electrical isolation between the individual contact pads.
  • the surfaces so treated are rinsed (e.g. with a solution of 5% HCl in water or 3% of citric acid in water) and the surfaces to be plated are now ready for bath immersion.
  • lead stabilizers such as, for example, lead acetate
  • the electroless plating baths which are utilized in accordance with an important aspect of this invention, contain lead salt levels from about 0.5 to about 2 ppm.
  • the electroless baths which are used in accordance with an important aspect of the present invention generally include a suitable nickel source, a borane reducing agent, an effective amount of an organic divalent sulfur compound which primarily functions as a bath stabilizer and, optionally, one or more additional stabilizers, buffers, buffering systems as well as wetting agents and other conventional bath ingredients.
  • the source of nickel cations for these nickel baths can be any of the water soluble or semi-soluble salts of nickel which are conventionally employed for such plating.
  • Suitable metal salts which can serve as sources of the nickel cations may, for example, include nickel acetate, nickel chloride, nickel sulfamate, nickel sulfate as well as other salts of nickel and other anions which are compatible with electroless nickel systems.
  • nickel glycolate as well as other nickel organic compounds can be used as the source of nickel ions in the bath.
  • Nickel concentrations utilized in these baths are those which are typical for electroless nickel plating baths and will generally range from about 0.05 mol per liter of bath to about 1 mol per liter.
  • the borane reducing agent utilized in these depositing baths include any bath soluble borane source such as the amine boranes, lower alkyl substituted amine boranes, and nitrogen-inclusive heterocyclic boranes including pyridine borane and morpholine borane. These compounds are typically characterized by their inclusion of a BH 3 group.
  • the alkylamine boranes are preferred, with dimethylamine borane being a particularly preferred reducing agent.
  • the reducing agent concentration used in these baths is such as to effect adequate reduction of the nickel cations within the bath under the operating conditions being employed.
  • a typical minimum concentration for the reducing agent can be as low as about 0.002 mol per liter of bath, but more usually, however, higher concentrations ranging from 0.01 to about 0.1 mol per liter will be employed with approximately 0.04 mol per liter being preferred for most operations.
  • bath concentrations thereof of from 1 to 5 grams per liter are generally satisfactory with a concentration of approximately 2.0 to 2.5 grams per liter being preferred.
  • These nickel plating baths in accordance with an important aspect of the present invention include an organic divalent sulfur compound which is soluble in the bath and wherein each of the two valences of the sulfur atom is directly linked with a carbon atom as a bath stabilizer.
  • suitable organic divalent sulfur compounds which are used in accordance with the present invention are the sulfur-containing aliphatic carboxylic acids, alcohols and their derivatives, the sulfur-containing aromatic/aliphatic carboxylic acids, the sulfur-containing acetylene compounds, the aromatic sulfides, the thiophenes and thionaphthenes, the thiazoles and thiourea.
  • Illustrative examples of these organic sulfur compounds are shown and described in U.S. Pat. No. 3,234,031.
  • Thiodiglycolic acid is a particularly preferred stabilizing agent for these nickel baths.
  • concentration of these sulfur-containing stabilizers will typically depend upon the particular stabilizer being employed and other bath conditions. Accordingly, effective amounts of such stabilisers can be described as those amounts which will effect the desired stability to the bath while at the same time enabling reduction of the nickel deposition onto the surfaces to be plated therein at the desired rate which will provide for, and enable the obtaining of, a nickel deposit of substantially uniform thickness, which is essentially free of irregularities in the surface without edge defects therein and which is also further characterized by being essentially crack-free. Concentrations of these sulfur-containing stabilizers will generally range from approximately 0.5 to 5 mmol per liter.
  • concentrations of such stabilizers in the bath of from approximately 25 to approximately 700 ppm can be utilized. Higher concentrations of such thiodiglycolic acid tend to substantially reduce the rate of deposition of the nickel and, accordingly, concentrations of approximately 50 to approximately 350 ppm of thiodiglycolic acid are preferred for most applications.
  • the nickel baths of the present invention can employ a wide variety of complexing agents, depending upon considerations such as availability, economics, and properties desired for the particular bath.
  • bath soluble carboxylic acids, substituted carboxylic acids, and bath soluble derivatives thereof, including hydroxy-substituted carboxylic acids, and bath soluble derivatives thereof including their anhydrides, salts or esters that are likewise bath soluble can be utilized.
  • Complexing agents which are suitable can also include ammonia and other organic complex-forming agents containing one or more of the following functional groups: primary amino groups, secondary amino groups, tertiary amino groups, imino groups, carboxy groups, and hydroxy groups.
  • preferred complexing agents include ethylenediamine, diethylenetriamine, triethylenetetramine, ethylenediaminetetraacetic acid, citric acid, lactic acid and water soluble salts thereof.
  • Related polyamines and N-carboxymethyl derivatives thereof may also be used.
  • the complexing agent bath concentration will normally be dependent upon the particular complexing agent or agents which are being used within the bath as well as upon the operating conditions of the bath.
  • the complexing agents will be present in the nickel baths of the present invention at a concentration of at least about 0.05 mol per liter, while concentrations as high as bath solubility limits and economic considerations dictate, usually no higher than about 1.5 mol per liter can be utilized, a typical concentration being between about 0.05 and about 1 mol per liter of bath, preferably being between about 0.1 and 0.7 mol per liter.
  • Buffers and buffering systems are typically included within the nickel bath of the present invention.
  • buffering agents must be those which are not antagonistic to the plating system. Both acidic and alkaline buffering systems are generally operative including the common carboxylic acids such as acetic acid, propionic acid and the like.
  • the bath may be buffered by adding a weak acid and its salts may be added in the desired amounts.
  • the amount of buffering agent or the buffering system which is present in these electroless nickel baths will vary depending upon conditions. A total concentration thereof of at least approximately 0.005 mol per liter is generally suitable. The concentration of such buffering agent or system, however, will vary in accordance with the needs for maintaining pH control and usually will not exceed approximately 0.4 mol per liter.
  • Suitable operating conditions for the nickel baths of the present invention will generally range from approximately 50° to 75° C., with a temperature of approximately 65° C. being commonly used in both barrel and rack plating operations. However, temperatures above or below these specific temperatures can be used to obtain acceptable nickel deposits on the preformed metallurgy patterns on substrate surfaces.
  • pH values for these baths will generally range from approximately 4.5 to approximately 7.5, with a pH of approximately 6.5 generally being preferred for most plating operations.
  • the nickel deposits which are achieved with the practice of the present invention can be characterized as high-purity nickel deposits, that is, deposits wherein the nickel concentration is at least 99.5 percent by weight with the remainder of the deposit being boron, sulfur, lead, carbon and being essentially free of other metals or contaminants.
  • the boron content is primarily controlled by the concentration of the organic divalent sulfur compound stabilizer which is present in the bath and that in lead free baths using the preferred thiodiglycolic acid in the preferred concentration, nickel having boron contents of from 0.1 to 0.2 percent will be readily obtained.
  • a multilayer ceramic module was fabricated utilizing an alumina ceramic material as previously described.
  • the top-side included contact pads and a seal band area, of a molybdenum conductive material, formed by screen printing a molybdenum and organic vehicle paste mixture on the surface of the green ceramic substrate prior to sintering. Upon sintering, the vehicle in the paste was burned off along with the binder resin in the substrate. The thickness of the molybdenum pads was 5 micrometers measured from the top surface of the substrate.
  • the sintered substrate was initially degreased with a vapor blast and then dipped for 45 seconds in an aequeous solution of 215 grams per liter of K 2 Fe(CN) 6 and 75 grams per liter of KOH.
  • the surface was then rinsed for one minute with deionized water and immersed in a hot potassium hydroxide solution having a concentration of 100 grams of potassium hydroxide per liter. This step was followed by a thorough rinsing with deionized water and the surface was then dipped in a 10 percent hydrochloric acid solution for 10 seconds followed by a thorough rinsing, again with deionized water.
  • the plating was continued for approximately 45 minutes until a nickel deposit of approximately 5.0 micrometers in thickness having a boron content of 0.1 weight percent was obtained.
  • the substrate so plated was then rinsed and observed to have a substantially uniform thickness over each of the contact pads and the seal bank area which deposits were observed to be crack-free and without any edge defects.
  • the individual contact pads were completely electrically isolated from each other and readily able to be joined by soldering or brazing to electrical component leads.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
US08/042,303 1992-04-06 1993-04-02 Process for providing catalytically active platinum metal layers Expired - Fee Related US5855959A (en)

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US08/443,132 US5624479A (en) 1993-04-02 1995-05-17 Solution for providing catalytically active platinum metal layers

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EP92105914A EP0564673B1 (de) 1992-04-06 1992-04-06 Verfahren zur Herstellung von katalytisch hochwirksamen Beschichtungen bestehend aus einem Metall der Gruppe der Platinmetalle
EP92105914 1992-06-04

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6717189B2 (en) * 2001-06-01 2004-04-06 Ebara Corporation Electroless plating liquid and semiconductor device
US20050170650A1 (en) * 2004-01-26 2005-08-04 Hongbin Fang Electroless palladium nitrate activation prior to cobalt-alloy deposition
WO2005111274A2 (en) 2004-04-30 2005-11-24 Macdermid, Incorporated Selective catalytic activation of non-conductive substrates
CN112663033A (zh) * 2020-12-16 2021-04-16 昆山成功环保科技有限公司 环保型化学沉镍溶液

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JP2001152840A (ja) 1999-11-24 2001-06-05 Honda Motor Co Ltd 多気筒内燃機関の排気系における触媒配置構造
JP4811543B2 (ja) * 2000-09-08 2011-11-09 学校法人早稲田大学 微細パターンの作製方法
JP2005126734A (ja) * 2003-10-21 2005-05-19 C Uyemura & Co Ltd 無電解ニッケルめっき浴及びそれを用いためっき方法

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US3234031A (en) * 1961-02-04 1966-02-08 Bayer Ag Reduction nickel plating with boron reducing agents and organic divalent sulfur stabilizers
US3958048A (en) * 1974-04-22 1976-05-18 Crown City Plating Company Aqueous suspensions for surface activation of nonconductors for electroless plating
US4004051A (en) * 1974-02-15 1977-01-18 Crown City Plating Company Aqueous noble metal suspensions for one stage activation of nonconductors for electroless plating
US4520046A (en) * 1983-06-30 1985-05-28 Learonal, Inc. Metal plating on plastics
US4704401A (en) * 1981-07-06 1987-11-03 Rorer Pharmaceutical Corporation Substituted phenyl amidinoureas
US4764401A (en) * 1981-12-05 1988-08-16 Bayer Aktiengesellschaft Process for activating substrate surfaces for electroless metallization

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US3011920A (en) * 1959-06-08 1961-12-05 Shipley Co Method of electroless deposition on a substrate and catalyst solution therefor
US3234031A (en) * 1961-02-04 1966-02-08 Bayer Ag Reduction nickel plating with boron reducing agents and organic divalent sulfur stabilizers
US4004051A (en) * 1974-02-15 1977-01-18 Crown City Plating Company Aqueous noble metal suspensions for one stage activation of nonconductors for electroless plating
US3958048A (en) * 1974-04-22 1976-05-18 Crown City Plating Company Aqueous suspensions for surface activation of nonconductors for electroless plating
US4704401A (en) * 1981-07-06 1987-11-03 Rorer Pharmaceutical Corporation Substituted phenyl amidinoureas
US4764401A (en) * 1981-12-05 1988-08-16 Bayer Aktiengesellschaft Process for activating substrate surfaces for electroless metallization
US4520046A (en) * 1983-06-30 1985-05-28 Learonal, Inc. Metal plating on plastics

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6717189B2 (en) * 2001-06-01 2004-04-06 Ebara Corporation Electroless plating liquid and semiconductor device
US20040157441A1 (en) * 2001-06-01 2004-08-12 Hiroaki Inoue Electroless plating liquid and semiconductor device
US6821902B2 (en) 2001-06-01 2004-11-23 Ebara Corporation Electroless plating liquid and semiconductor device
US20050170650A1 (en) * 2004-01-26 2005-08-04 Hongbin Fang Electroless palladium nitrate activation prior to cobalt-alloy deposition
WO2005111274A2 (en) 2004-04-30 2005-11-24 Macdermid, Incorporated Selective catalytic activation of non-conductive substrates
CN112663033A (zh) * 2020-12-16 2021-04-16 昆山成功环保科技有限公司 环保型化学沉镍溶液

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JPH0610146A (ja) 1994-01-18
DE69205415D1 (de) 1995-11-16
EP0564673A1 (de) 1993-10-13
EP0564673B1 (de) 1995-10-11
DE69205415T2 (de) 1996-05-30

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